EP0522585B1 - Process of fabricating porous silicone product - Google Patents
Process of fabricating porous silicone product Download PDFInfo
- Publication number
- EP0522585B1 EP0522585B1 EP92111794A EP92111794A EP0522585B1 EP 0522585 B1 EP0522585 B1 EP 0522585B1 EP 92111794 A EP92111794 A EP 92111794A EP 92111794 A EP92111794 A EP 92111794A EP 0522585 B1 EP0522585 B1 EP 0522585B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- water
- organopolysiloxane
- parts
- porous silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001296 polysiloxane Polymers 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 19
- 239000000839 emulsion Substances 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 239000008119 colloidal silica Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 125000005372 silanol group Chemical group 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 229920001971 elastomer Polymers 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- 239000000806 elastomer Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 description 30
- -1 i.e. Substances 0.000 description 19
- 239000004205 dimethyl polysiloxane Substances 0.000 description 15
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 15
- 238000007710 freezing Methods 0.000 description 11
- 230000008014 freezing Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000010257 thawing Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 239000000945 filler Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- QMEAARYBLDUJTM-UHFFFAOYSA-N [methyl-di(propanoyloxy)silyl] propanoate Chemical compound CCC(=O)O[Si](C)(OC(=O)CC)OC(=O)CC QMEAARYBLDUJTM-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000013023 gasketing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- JUYONNFUNDDKBE-UHFFFAOYSA-J tri(oct-2-enoyloxy)stannyl oct-2-enoate Chemical compound [Sn+4].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O JUYONNFUNDDKBE-UHFFFAOYSA-J 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- RVXKJRWBHPHVOV-UHFFFAOYSA-L zinc;oct-2-enoate Chemical compound [Zn+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O RVXKJRWBHPHVOV-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
- B01D71/701—Polydimethylsiloxane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/14—Ageing features
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
Definitions
- the present invention is directed to a process of fabricating a porous silicone product, and more particularly to a porous silicone membrane for use in membrane separation of a liquid component for a liquid solution containing two or more liquid components.
- Japanese Patent Publication (KOKOKU) No. 62-49897 discloses a process of fabricating a porous silicone product.
- the process comprises to firstly freeze a water emulsion of organopolysiloxane into a resulting frozen body followed by defrosting the frozen body to obtain a wet and spongy elastomer. Thereafter, the resulting elastomer is dried to remove the water content to thereby obtain a porous silicone product. Since this process comprises simple steps of freezing, defrosting and drying, the porous silicone product can be easily fabricated. However, the process is found to be only effective to fabricate the silicon product with closed or non-intercommunicating cells, and is not applicable to fabricate a silicone product with open or intercommunicating cells.
- the silicone product fabricated by the process disclosed in the above publication is effective as a gasket or a heat insulation member which requires to have the closed cells, but can not be utilized as a filter or the like which necessitates open cells, for example, as a membrane filter for separation of a liquid component from a liquid solution containing two or more liquid components.
- EP-A-0 097 914 discloses a very similar method of producing silicone elastomeric sponge.
- the method comprises freezing an aqueous silicone emulsion, then thawing and drying to produce a silicone sponge.
- the aqueous silicone emulsion comprises an ionically stabilized hydroxyl and blocked polydiorganosiloxane, an organic tin compound, a colloidal silica, and water.
- the sponge produced by this method contains irregular closed cells like those generated by the process disclosed in Japanese Patent Publication (KOKOKU) No. 62-49897 and is usefull as insulation and gasketing at high and low temperatures.
- WPIL-abstract AN 89058211 [08] discloses a method for the production of a porous article of hydrophilic polymers, e.g. casein, cellulose or polyvinylalcohol, having open pores. To realize this, the hydrophilic polymer or a mixture therefrom and a surfactant which does not cause coagulation reaction with the hydrophilic polymer is completely frozen and then dried.
- hydrophilic polymers e.g. casein, cellulose or polyvinylalcohol
- the present invention has been accomplished to eliminate the above problem and has a primary object to provide a unique method of fabricating a porous silicone product with open cells.
- the present invention is related to a process of fabricating a porous silicone product utilizing a water emulsion of an organopolysiloxane, said process comprising the steps of: preparing an emulsion including:
- a preferred embodiment of the present invention can be taken from claim 2.
- the water emulsion i.e., water emulsion of a water-emulsifiable organopolysiloxane may include the one disclosed in Japanese Patent Publication (kokoku) No 62-49897 or like emulsions known in the art.
- kokoku Japanese Patent Publication
- following known emulsions may be utilized in the present invention.
- the emulsion contains the followings in order to expedite curing by removal of water at room temperatures into a resulting elastomer;
- Organopolysiloxane as defined in the above (a) is a polymer having at least two silanol groups per one molecule and is cross-linked by the cross-linking agent (b) into a rubber elastic body.
- the location of the silanol groups is not limited, the silanol groups are preferred to locate at the terminal chain ends of the polymer.
- Organic groups bonded to the silicon atoms of the organopolysiloxane are of monovalent hydrocarbon substituent or non-substituent groups which include alkyl group such as methyl, ethyl, propyl and butyl group; alkenyl group such as vinyl and allyl group; aryl group such as phenyl group; aralkyl group such as benzyl group; alkaryl group such as styryl, tolyl group; cycloalkyl group such as cyclohexyl, cyclopentyl group; or any one of the above groups in which hydrogen atoms are partially or entirely substituted by halogen of fluorine, chlorine or bromine, for example, 3,3,3-trifluoropropyl group.
- alkyl group such as methyl, ethyl, propyl and butyl group
- alkenyl group such as vinyl and allyl group
- aryl group such as phenyl group
- the monovalent hydrocarbon groups it is general to use methyl, vinyl or phenyl groups, among all, methyl groups.
- the monovalent hydrocarbon groups bonded to the silicon atoms may be identical or combination of different ones from each other.
- Organopolysiloxane is of substantially straight chain structure which may include some rather branch chains. Although organopolysiloxane is not limited to have a definite molecular weight, it is preferred to have a molecular weight of 5000 or more. This is because of the fact that desired tensile strength and elongation is obtained at a molecular weight of 5000 or more.
- Such organopolysiloxane may include dimethylpolysiloxane of which terminal ends are closed by silanol groups, methylphenylpolysiloxane, copolymer of dimethylsiloxane and methylyphenylsiloxane, methylvinylpolysiloxane, and copolymer of dimethylsiloxane and methylvinylsiloxane.
- the above organopolysiloxane may be synthesized for example, by ring-opening polymerization of cyclodiorganosiloxane, by hydrolysis condensation of straight or branch chain organopolysiloxane having hydrolyzable alkoxy or acyloxy groups, or by hydrolysis of one or more diorganodihalogenosilanes.
- the cross-linking agent constitutes a cross-linking of the above mentioned organopolysiloxane and may include colloidal silica, silicate of alkali metal, hydrolyzable silane, and partially hydrolyzed condensate of hydrolyzable silane.
- the colloidal silica may be fumed colloidal silica, precipitation colloidal silica, or colloidal silica stabilized with Na, NH3, or Al ions and having a particle size of 0.0001 to 0.1 ⁇ m.
- the amount of the colloidal silica is 1 to 150, more preferably 1 to 70, parts by weight of the colloidal silica is utilized for 100 parts by weight of the above organopolysiloxane.
- the silicate of alkali metal is preferred to be of water soluble and is prepared in an aqueous solution thereof.
- the silicate of alkali metal includes lithium silicate, sodium silicate, potassium silicate, and rubidium silicate.
- the amount of silicate of alkali metal preferably ranges from 0.3 to 30 parts by weight, more preferably, from 0.3 to 20 parts by weight for 100 parts by weight of organopolysiloxane.
- Hydrolyzable silane and partially hydrolyzed condensate of hydrolyzable silane are required to have in one molecule thereof at least three hydrolyzable groups bonded to the silicon atoms because of that an elastomer is not obtained with two or less hydrolyzable groups.
- the hydrolyzable group includes alkoxy group such as methoxy, ethoxy, and butoxy group; acyloxy group such as acetoxy group; substituted or non-substituted group such as acetoamide group and N-methylacetoamido group; substituted amino group such as N,N-diethylamino group; and ketoxime group such as methylethlyketoxime group.
- Examples of the cross-linking agent are methyltriethoxysilane, vinyltrimethoxysilane, normalpropylorthosilicate, ethylpolysilicate, propylpolysilicate, methyltri(propanoxy)silane, methyltri(methylethylketoxime)silane. Combination of two or more such cross-linking agents may be used.
- the amount of the cross-linking agent ranges preferably from 1 to 150 parts by weight for 100 parts by weight of organopolysiloxane.
- the above curing catalyst is employed to promote the cross-linking of organopolysiloxane by the cross-linking agent and include metal salt of organic acid such as dibutyl-tin-dilaurate, dibutyl-tin-diacetate, tin octenate, dibutyl-tin-dioctate, tin laurate, ferric stannooctenate, lead octanate, lead laurate, and zinc octenate; titanic acid ester such as tetrabutyltitanate, tetrapropyltitanate, dibutoxytitan-bis(ethylacetoacetate); and amine compound or hydrochlorate of n-hexylamine and guanidine.
- metal salt of organic acid such as dibutyl-tin-dilaurate, dibutyl-tin-diacetate, tin octenate, dibutyl-tin-di
- the curing catalyst is preferably made in advance into an emulsion with an aid of an emulsifier and water by a conventional method.
- the amount of the curing agent ranges preferably from 0.01 to 1.5, more preferably, from 0.05 to 1 parts by weight for 100 parts by weight of organopolysiloxane.
- the above emulsifier for emulsifying the organopolysiloxane may be anionic, non-inonic or cationic emulsifier.
- the anionic emulsifier includes, for example, salts of higher fatty acids, salts of sulfuric acid esters of higher alcohols, alkylbenzenesulfonate, alkylnaphthalenesulfonate, and alkylsulfonate, polyethyleneglycolsulfate.
- the non-ionic emulsifier includes, for example, polyoxyethylenealkylphenylether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyethylene polyoxypropylen, and monoglyceride of fatty acid.
- the cationic emulsifier includes, for example, aliphatic amine salts, quaternary ammonium salt and alkylpyridinum salts. One or more of these emulsifier may be utilized for preparation of the emulsion.
- the amount of the emulsifier ranges preferably from 2 to 30 parts by weight for 100 parts by weight of organopolysiloxane.
- Water is utilized in sufficient amount to prepare an aqueous emulsion of organopolysiloxane with the cross-linking agent, the curing catalyst and the emulsifier. Therefore, no limitation is made to the amount of water.
- An emulsion of the organopolysiloxane which forms an elastomer by removal of water therefrom can be prepared from the aqueous emulsion of the organopolysiloxane, the cross-linking agent, curing catalyst, emulsifier and water in accordance with one of known processes.
- the aqueous emulsion can be made by utilizing an emulsifying device such as a homomixer, homogenizer, or colloid mill to emulsify dimethylpolysiloxane having silanol groups at its terminal ends into water with the emulsifier followed by adding and mixing the curing catalyst such as colloidal silica.
- the aqueous emulsion is prepared by emulsifying cyclodiorganosiloxane, for example, octamethylcyclotetrasiloxane into water by the emulsifier, adding an open-ring polymerization catalyst to proceed polymerization under the application of heat for preparing dimethylpolysiloxane of which terminal ends are blocked by silanol groups followed by adding and mixing the cross-linking agent, for example, colloidal silica and the curing catalyst.
- cyclodiorganosiloxane for example, octamethylcyclotetrasiloxane into water by the emulsifier
- an open-ring polymerization catalyst to proceed polymerization under the application of heat for preparing dimethylpolysiloxane of which terminal ends are blocked by silanol groups
- the cross-linking agent for example, colloidal silica and the curing catalyst.
- a base emulsion which consists essentially of: 100 parts by weight of organopolysiloxane containing silanol groups; 1 to 150 parts by weight of colloidal silica, 0.3 to 30 parts by weight of silicate of metal alkali, or 1 to 150 parts by weight of hydrolyzable silane or partially hydrolyzed condensate thereof as the cross-linking agent; 0.01 to 1.5 parts by weight of the curing catalyst; 2 to 30 parts by weight of the emulsifier; and water.
- the resulting base emulsion is adjusted to have a 9 to 12 pH by a suitable pH adjustor to provide a resulting aqueous emulsion of organopolysiloxane of excellent shelf life stability.
- the pH adjustor includes amines such as dimethylamine and ethyleneamine, and hydroxides of alkali metal such as sodium hydroxide and potassium hydroxide.
- organic amines are selected as the pH adjustor.
- Such organic amines includes, in addition to the above, monoethanolamine, triethanolamine, morpholine and 2-amino-2-methyl-1-propanol.
- the aging temperature is selected so as not to destroy the emulsion and is preferably from 10 to 95 °C, and more preferably from 15 to 50 °C.
- the aging time period is selected in accordance with the aging temperature and is preferably, for example, a week or more at the aging temperature of 25 °C and 4 days or more at 40 °C.
- the base emulsion may have the pH of 9 or less.
- the organopolysiloxane emulsion in accordance with the present invention may additionally include a thickening agent, filler, pigment, dye, heat-resisting agent, antiseptic, penetrant such as aqueous ammonia in a suitable amount.
- the emulsion is prepared to include the cross-linking agent other than the colloidal silica, the resulting organopolysiloxane shows less viscosity and is difficult to be formed into thick elastomer.
- the filler such as quartz powder, calcium carbonate, magnesium oxide, zinc dioxide, titanium dioxide and carbon black.
- the filler is preferably provided in the form of a colloid.
- the thickening agent includes carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinylalcohol, and polyacrylic acid.
- the organopolysiloxane emulsion is frozen within a freezer.
- the emulsion may be spread over a flat plate, or poured onto a flat bottom of a container to form a layer of uniform thickness, prior to the freezing.
- the cooling temperature is preferably set to a temperature which is higher only by 2 to 3 °C than the freezing point of the organopolysiloxane emulsion.
- the cooling is preferably kept continued for a time period of 1 to 5 hours.
- the emulsion having a freezing point of - 10 °C is cooled in a cooled vessel maintained at a temperature of -7 to -8 °C for approximately 3 hours. Freezing of the emulsion without such preliminary cooling will cause stratification between water and solid content within the emulsion, thereby making it difficult to obtain the silicone product with uniform porosity. Also with this direct freezing, the water crystal, i.e. ice becomes into large size, which makes it difficult to obtain the porous silicone product with fine and dense cells.
- the organopolysiloxane emulsion is frozen within the freezer.
- the freezing temperature may be as low as possible, and is selected to be a temperature which is lower by 5 °C or more, preferably 10 °C or more than the freezing point of the emulsion. With this freezing, the water contained in the organopolysiloxane emulsion is frozen to be separated therefrom, thereby allowing to react organopolysiloxane with the cross-linking agent, enhancing it into three-dimensional structure to result a silicone elastomer.
- the silicone elastomer is dried without being defrosted in order to sublime the water content from the ice.
- Such drying is performed in vacuum with the silcone elastomer placed in a vacuum chamber of a freeze-drying device while recovering the water in a cold-trap manner.
- emulsion B containing the curing catalyst.
- 100 parts of emulsion A were mixed with 1.5 parts of emulsion B and 25 parts of aqueous dissipation solution of colloidal silica (having a solid content of 30 wt%) as the cross-linking agent.
- Diethylamine was added for adjusting the pH of the resulting mixture to 11, after which the mixture was aged at a room temperature of 25 °C for 2 weeks to obtain a dimethylpolysiloxane emulsion.
- the Petri dish was sealed at its top opening by an aluminum foil to effect preliminarily cooling the specimen at a temperature of -6 °C for 3 hours.
- the specimen was placed into a freezer maintained at a temperature of - 25 °C and kept for 15 hours to be frozen therein.
- FIGS. 1 and 2 show cross-sections of thus obtained silicone membrane in photomicrographs.
- emulsion A prepared in Example 1 100 parts were mixed with 1.5 parts of emulsion B prepared in Example 1, and 25 parts of aqueous dissipation solution of colloidal silica (having a solid content of 30 wt%) as the cross-linking agent to provide a dimethylpolysiloxane emulsion having the pH of 5.5. Thereafter, dimethylpolysiloxane emulsion was frozen and dried in the same manner as in Example 1 to provide a 2 mm thick porous silicone membrane except for that the emulsion has not been aged prior to the freeze-drying. The resulting silicone membrane was found to have a number of open cells having an average diameter of 30 ⁇ m and intercommunicated through voids of 1.5 ⁇ m in average diameter.
- emulsion A prepared in Example 1 100 parts were mixed with 1.5 parts of emulsion B prepared in Example 1, and 3 parts of sodium silicate as a curing catalyst. After being added with diethylamine for pH adjustment to 10, the mixture was aged at a room temperature of 25 °C for 4 weeks to prepare a dimethylpolysiloxane emulsion.
- emulsion was then frozen and dried in the same manner as in Example 1 to provide a 2 mm thick porous silicone membrane except for that the emulsion has not been aged prior to the freeze-drying.
- the resulting silicone membrane was found to have a number of open cells having an average diameter of 40 ⁇ m and intercommunicated through voids of 1.5 ⁇ m in average diameter.
- emulsion A prepared in Example 1 100 parts were mixed with 1 part of vinyltrimethoxysilane as a cross-linking agent and 0.1 part of dioctyl-tin-dilaurate as a curing catalyst followed by being stirred into a homogeneous emulsion of dimethylpolysiloxane.
- emulsion was then frozen and dried in the same manner as in Example 1 to provide a 2 mm thick porous silicone membrane except for that the emulsion has not been aged prior to the freezedrying.
- the resulting silicone membrane was found to have a number of open cells having an average diameter of 20 ⁇ m and intercommunicated through voids of 1 ⁇ m in average diameter.
- the dimethylpolysiloxane emulsion prepared in Example 1 was defoamed and poured onto the Petri dish to form a specimen of 2 mm thickness.
- the specimen was placed in the freezer maintained at a temperature of - 20 °C and kept for 16 hours to be frozen therein. After removing out of the freezer, the specimen was left standing at a room temperature of 25 °C for 6 hours so as to be defrosted into a 2 mm thick silicone membrane saturated with water. Next, thus defrosted silicone membrane was dried within an oven of 70 °C for 20 hours to obtain a 1.1 mm thick porous silicone membrane.
- the resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 70 ⁇ m and also found to have a skin layer on its surface.
- the dimethylpolysiloxane emulsion prepared in Example 2 was treated in the identical manner as in Comparative Example 1 to provide a 1 mm thick porous silicone membrane.
- the resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 30 ⁇ m and also found to have a skin layer on its surface.
- the dimethylpolysiloxane emulsion prepared in Example 3 was treated in the identical manner as in Comparative Example 1 to provide a 1 mm thick porous silicone membrane.
- the resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 40 ⁇ m and also found to have a skin layer on its surface.
- the dimethylpolysiloxane emulsion prepared in Example 4 was treated in the identical manner as in comparative Example 1 to provide a 1.1 mm thick porous silicone membrane.
- the resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 20 ⁇ m and also found to have a skin layer on its surface.
Description
- The present invention is directed to a process of fabricating a porous silicone product, and more particularly to a porous silicone membrane for use in membrane separation of a liquid component for a liquid solution containing two or more liquid components.
- Japanese Patent Publication (KOKOKU) No. 62-49897 discloses a process of fabricating a porous silicone product. The process comprises to firstly freeze a water emulsion of organopolysiloxane into a resulting frozen body followed by defrosting the frozen body to obtain a wet and spongy elastomer. Thereafter, the resulting elastomer is dried to remove the water content to thereby obtain a porous silicone product. Since this process comprises simple steps of freezing, defrosting and drying, the porous silicone product can be easily fabricated. However, the process is found to be only effective to fabricate the silicon product with closed or non-intercommunicating cells, and is not applicable to fabricate a silicone product with open or intercommunicating cells. This means that the silicone product fabricated by the process disclosed in the above publication is effective as a gasket or a heat insulation member which requires to have the closed cells, but can not be utilized as a filter or the like which necessitates open cells, for example, as a membrane filter for separation of a liquid component from a liquid solution containing two or more liquid components.
- EP-A-0 097 914 discloses a very similar method of producing silicone elastomeric sponge. The method comprises freezing an aqueous silicone emulsion, then thawing and drying to produce a silicone sponge. The aqueous silicone emulsion comprises an ionically stabilized hydroxyl and blocked polydiorganosiloxane, an organic tin compound, a colloidal silica, and water. The sponge produced by this method contains irregular closed cells like those generated by the process disclosed in Japanese Patent Publication (KOKOKU) No. 62-49897 and is usefull as insulation and gasketing at high and low temperatures.
- WPIL-abstract AN 89058211 [08] discloses a method for the production of a porous article of hydrophilic polymers, e.g. casein, cellulose or polyvinylalcohol, having open pores. To realize this, the hydrophilic polymer or a mixture therefrom and a surfactant which does not cause coagulation reaction with the hydrophilic polymer is completely frozen and then dried.
- The present invention has been accomplished to eliminate the above problem and has a primary object to provide a unique method of fabricating a porous silicone product with open cells.
- The present invention is related to a process of fabricating a porous silicone product utilizing a water emulsion of an organopolysiloxane, said process comprising the steps of: preparing an emulsion including:
- a) a substantially straight chain organopolysiloxane having at least two silanol groups per one molecule;
- b) a cross-linking agent selected from colloidal silica, alkali metal silicate and hydrolyzable silane and partially hydrolyzed condensate of hydrolyzable silane, having at least three hydrolyzable groups attached to silicon atoms;
- c) a curing catalyst;
- d) an emulsifier; and
- e) water,
- A preferred embodiment of the present invention can be taken from claim 2.
-
- FIG. 1 is a photomicrograph showing a cross section of a porous silicone membrane obtained in Example 1 at 50 times magnification; and
- FIG. 2 is an electron photomicrograph showing the cross section of the above the silicone membrane at 250 times magnification.
- The present invention will be discussed in detail. The water emulsion, i.e., water emulsion of a water-emulsifiable organopolysiloxane may include the one disclosed in Japanese Patent Publication (kokoku) No 62-49897 or like emulsions known in the art. For example, following known emulsions may be utilized in the present invention. A mixture emulsion of diorganopolysiloxane with silanol groups, colloidal silica and organic tin catalyst, as disclosed in Japanese Early Patent Publication (KOKAI) No.56-16553. A mixture containing an emulsion of diorganopolysiloxane with vinyl groups, an emulsion of organohydrodienepolysiloxane, and platinum catalyst, as disclosed in Japanese Early Patent Publication (KOKAI) No. 56-36546. A polymerization emulsion of cyclodiorganosiloxane and functional organic alkoxysilane as disclosed in Japanese Patent Publication (KOKOKU) No. 56-38609. A mixture emulsion of diorganopolysiloxane with silanol groups, hydrolyzable silane and curing catalyst, as disclosed in Japanese Patent Publication (KOKOKU) No. 59-36677.
- The emulsion contains the followings in order to expedite curing by removal of water at room temperatures into a resulting elastomer;
- a) substantially straight chain organopolysiloxane having at least two silanol groups per one molecule;
- b) a cross-linking agent selected from the group consisting of colloidal silica, silicate of alkali metal, hydrolyzable silane, and partially hydrolyzed condensate of hydrolyzable silane;
- c) curing catalyst;
- d) emulsifier; and
- e) water.
- Organopolysiloxane as defined in the above (a) is a polymer having at least two silanol groups per one molecule and is cross-linked by the cross-linking agent (b) into a rubber elastic body. Although the location of the silanol groups is not limited, the silanol groups are preferred to locate at the terminal chain ends of the polymer. Organic groups bonded to the silicon atoms of the organopolysiloxane are of monovalent hydrocarbon substituent or non-substituent groups which include alkyl group such as methyl, ethyl, propyl and butyl group; alkenyl group such as vinyl and allyl group; aryl group such as phenyl group; aralkyl group such as benzyl group; alkaryl group such as styryl, tolyl group; cycloalkyl group such as cyclohexyl, cyclopentyl group; or any one of the above groups in which hydrogen atoms are partially or entirely substituted by halogen of fluorine, chlorine or bromine, for example, 3,3,3-trifluoropropyl group. As the monovalent hydrocarbon groups, it is general to use methyl, vinyl or phenyl groups, among all, methyl groups. The monovalent hydrocarbon groups bonded to the silicon atoms may be identical or combination of different ones from each other. Organopolysiloxane is of substantially straight chain structure which may include some rather branch chains. Although organopolysiloxane is not limited to have a definite molecular weight, it is preferred to have a molecular weight of 5000 or more. This is because of the fact that desired tensile strength and elongation is obtained at a molecular weight of 5000 or more.
- Such organopolysiloxane may include dimethylpolysiloxane of which terminal ends are closed by silanol groups, methylphenylpolysiloxane, copolymer of dimethylsiloxane and methylyphenylsiloxane, methylvinylpolysiloxane, and copolymer of dimethylsiloxane and methylvinylsiloxane. The above organopolysiloxane may be synthesized for example, by ring-opening polymerization of cyclodiorganosiloxane, by hydrolysis condensation of straight or branch chain organopolysiloxane having hydrolyzable alkoxy or acyloxy groups, or by hydrolysis of one or more diorganodihalogenosilanes.
- The cross-linking agent constitutes a cross-linking of the above mentioned organopolysiloxane and may include colloidal silica, silicate of alkali metal, hydrolyzable silane, and partially hydrolyzed condensate of hydrolyzable silane. The colloidal silica may be fumed colloidal silica, precipitation colloidal silica, or colloidal silica stabilized with Na, NH3, or Al ions and having a particle size of 0.0001 to 0.1 µm. The amount of the colloidal silica is 1 to 150, more preferably 1 to 70, parts by weight of the colloidal silica is utilized for 100 parts by weight of the above organopolysiloxane. The silicate of alkali metal is preferred to be of water soluble and is prepared in an aqueous solution thereof. The silicate of alkali metal includes lithium silicate, sodium silicate, potassium silicate, and rubidium silicate. The amount of silicate of alkali metal preferably ranges from 0.3 to 30 parts by weight, more preferably, from 0.3 to 20 parts by weight for 100 parts by weight of organopolysiloxane. Hydrolyzable silane and partially hydrolyzed condensate of hydrolyzable silane are required to have in one molecule thereof at least three hydrolyzable groups bonded to the silicon atoms because of that an elastomer is not obtained with two or less hydrolyzable groups. The hydrolyzable group includes alkoxy group such as methoxy, ethoxy, and butoxy group; acyloxy group such as acetoxy group; substituted or non-substituted group such as acetoamide group and N-methylacetoamido group; substituted amino group such as N,N-diethylamino group; and ketoxime group such as methylethlyketoxime group. Examples of the cross-linking agent are methyltriethoxysilane, vinyltrimethoxysilane, normalpropylorthosilicate, ethylpolysilicate, propylpolysilicate, methyltri(propanoxy)silane, methyltri(methylethylketoxime)silane. Combination of two or more such cross-linking agents may be used. The amount of the cross-linking agent ranges preferably from 1 to 150 parts by weight for 100 parts by weight of organopolysiloxane.
- The above curing catalyst is employed to promote the cross-linking of organopolysiloxane by the cross-linking agent and include metal salt of organic acid such as dibutyl-tin-dilaurate, dibutyl-tin-diacetate, tin octenate, dibutyl-tin-dioctate, tin laurate, ferric stannooctenate, lead octanate, lead laurate, and zinc octenate; titanic acid ester such as tetrabutyltitanate, tetrapropyltitanate, dibutoxytitan-bis(ethylacetoacetate); and amine compound or hydrochlorate of n-hexylamine and guanidine. The curing catalyst is preferably made in advance into an emulsion with an aid of an emulsifier and water by a conventional method. The amount of the curing agent ranges preferably from 0.01 to 1.5, more preferably, from 0.05 to 1 parts by weight for 100 parts by weight of organopolysiloxane.
- The above emulsifier for emulsifying the organopolysiloxane may be anionic, non-inonic or cationic emulsifier. The anionic emulsifier includes, for example, salts of higher fatty acids, salts of sulfuric acid esters of higher alcohols, alkylbenzenesulfonate, alkylnaphthalenesulfonate, and alkylsulfonate, polyethyleneglycolsulfate. The non-ionic emulsifier includes, for example, polyoxyethylenealkylphenylether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyethylene polyoxypropylen, and monoglyceride of fatty acid. The cationic emulsifier includes, for example, aliphatic amine salts, quaternary ammonium salt and alkylpyridinum salts. One or more of these emulsifier may be utilized for preparation of the emulsion. The amount of the emulsifier ranges preferably from 2 to 30 parts by weight for 100 parts by weight of organopolysiloxane.
- Water is utilized in sufficient amount to prepare an aqueous emulsion of organopolysiloxane with the cross-linking agent, the curing catalyst and the emulsifier. Therefore, no limitation is made to the amount of water.
- An emulsion of the organopolysiloxane which forms an elastomer by removal of water therefrom can be prepared from the aqueous emulsion of the organopolysiloxane, the cross-linking agent, curing catalyst, emulsifier and water in accordance with one of known processes. For example, the aqueous emulsion can be made by utilizing an emulsifying device such as a homomixer, homogenizer, or colloid mill to emulsify dimethylpolysiloxane having silanol groups at its terminal ends into water with the emulsifier followed by adding and mixing the curing catalyst such as colloidal silica. Alternately, the aqueous emulsion is prepared by emulsifying cyclodiorganosiloxane, for example, octamethylcyclotetrasiloxane into water by the emulsifier, adding an open-ring polymerization catalyst to proceed polymerization under the application of heat for preparing dimethylpolysiloxane of which terminal ends are blocked by silanol groups followed by adding and mixing the cross-linking agent, for example, colloidal silica and the curing catalyst.
- For excellent shelf life stability, it is preferred to firstly prepare a base emulsion which consists essentially of: 100 parts by weight of organopolysiloxane containing silanol groups; 1 to 150 parts by weight of colloidal silica, 0.3 to 30 parts by weight of silicate of metal alkali, or 1 to 150 parts by weight of hydrolyzable silane or partially hydrolyzed condensate thereof as the cross-linking agent; 0.01 to 1.5 parts by weight of the curing catalyst;
2 to 30 parts by weight of the emulsifier; and
water.
The resulting base emulsion is adjusted to have a 9 to 12 pH by a suitable pH adjustor to provide a resulting aqueous emulsion of organopolysiloxane of excellent shelf life stability. The pH adjustor includes amines such as dimethylamine and ethyleneamine, and hydroxides of alkali metal such as sodium hydroxide and potassium hydroxide. Preferably, organic amines are selected as the pH adjustor. Such organic amines includes, in addition to the above, monoethanolamine, triethanolamine, morpholine and 2-amino-2-methyl-1-propanol. After the pH adjustment, the emulsion is aged for a predetermined time period at a constant temperature. The aging temperature is selected so as not to destroy the emulsion and is preferably from 10 to 95 °C, and more preferably from 15 to 50 °C. The aging time period is selected in accordance with the aging temperature and is preferably, for example, a week or more at the aging temperature of 25 °C and 4 days or more at 40 °C. Thus obtained emulsion of organopolysiloxane exhibits excellent shelf life stability at room temperatures and is easy to cure into an elastomer at the room temperatures by removal of water therefrom. - When the shelf life stability at room temperatures is not required, the base emulsion may have the pH of 9 or less. The organopolysiloxane emulsion in accordance with the present invention may additionally include a thickening agent, filler, pigment, dye, heat-resisting agent, antiseptic, penetrant such as aqueous ammonia in a suitable amount. When the emulsion is prepared to include the cross-linking agent other than the colloidal silica, the resulting organopolysiloxane shows less viscosity and is difficult to be formed into thick elastomer. To avoid this insufficiency, it is preferred to additionally incorporate the filler such as quartz powder, calcium carbonate, magnesium oxide, zinc dioxide, titanium dioxide and carbon black. In order to give an increased tension strength as well as elongation to the resulting elastomer, the filler is preferably provided in the form of a colloid. The thickening agent includes carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinylalcohol, and polyacrylic acid.
- Prior to fabricating a porous silicon product with open cells from thus obtained organopolysiloxane emulsion, it is required to remove foams out of the emulsion by, for example, the vacuum defoaming process. Without the defoaming, the foams are likely to be left entrapped in the resulting porous silicone product, which fails to obtain the silicone product with uniform porosity. Especially when the silicone product is made into a membrane, the foams are cause of large holes in the membrane. With this result, when the membrane is utilized as a selective permeable membrane for separation of a liquid component from a solution containing two or more liquid components, good separation efficiency will not expected by the presence of the large holes in the membrane.
- After defoaming, the organopolysiloxane emulsion is frozen within a freezer. For fabrication of the silicone membrane, the emulsion may be spread over a flat plate, or poured onto a flat bottom of a container to form a layer of uniform thickness, prior to the freezing. Also prior to the freezing, it is preferred to effect preliminary cooling of the emulsion down to such a minimum possible temperature as not to freeze the emulsion and to keep cooling over a predetermined period of time. For example, the cooling temperature is preferably set to a temperature which is higher only by 2 to 3 °C than the freezing point of the organopolysiloxane emulsion. The cooling is preferably kept continued for a time period of 1 to 5 hours. For example, the emulsion having a freezing point of - 10 °C is cooled in a cooled vessel maintained at a temperature of -7 to -8 °C for approximately 3 hours. Freezing of the emulsion without such preliminary cooling will cause stratification between water and solid content within the emulsion, thereby making it difficult to obtain the silicone product with uniform porosity. Also with this direct freezing, the water crystal, i.e. ice becomes into large size, which makes it difficult to obtain the porous silicone product with fine and dense cells.
- After the preliminary cooling, the organopolysiloxane emulsion is frozen within the freezer. The freezing temperature may be as low as possible, and is selected to be a temperature which is lower by 5 °C or more, preferably 10 °C or more than the freezing point of the emulsion. With this freezing, the water contained in the organopolysiloxane emulsion is frozen to be separated therefrom, thereby allowing to react organopolysiloxane with the cross-linking agent, enhancing it into three-dimensional structure to result a silicone elastomer.
- Thereafter, the silicone elastomer is dried without being defrosted in order to sublime the water content from the ice. Such drying is performed in vacuum with the silcone elastomer placed in a vacuum chamber of a freeze-drying device while recovering the water in a cold-trap manner. The vacuum drying is preferably carried out within the vacuum chamber under the vacuum pressure of 1 Torr (=̂ 133 Pa) or less for a time period of at least 4 hours. As a result of subliming the water content from the silicone elastomer, corresponding voids are left within the silicone elastomer such that the resulting elastomer has a number of open or intercommunicating cells. This is very opposite to the case where the silicone product with closed or non-intercommunicating cells is obtained as a consequence of defrosting the silicone elastomer prior to the drying. Accordingly, it should be required to effect drying as soon as possible so as to avoid defrosting the frozen silicone elastomer. Any heating should be avoided at the initial stage of the drying. However, it may be advantageous to apply the heat at the final stage of the drying for promoting and completing the drying.
- The following Examples are further illustrative of this invention. All parts are by weight.
- 100 parts of dimethylpolysiloxane having 30 as repeating number of siloxane units and having its terminal end closed by silanol groups were mixed with 2 parts of sodium lauryl sulfate and 70 parts of water. The resulting mixture was passed twice through a homogenizer under a pressure of 150 kg/cm2. Then, 1 part of dodecylbenzenesulfonic acid was added as a polymerization initiator to the mixture followed by being subject to emulsion polymerization at a room temperature for 16 hours, after which a solution of sodium hydroxide is utilized to adjust the pH of the mixture to 7, thereby preparing an emulsion A containing dimethylpolysiloxane having a molecular weight of 200,000 and having its terminal ends blocked by the silanol groups.
- 40 parts of dioctyl-tin-dilaurate were mixed with 10 parts of sodium lauryl sulfate and 40 parts of water followed by being passed twice through the homogenizer to prepare an emulsion B containing the curing catalyst. 100 parts of emulsion A were mixed with 1.5 parts of emulsion B and 25 parts of aqueous dissipation solution of colloidal silica (having a solid content of 30 wt%) as the cross-linking agent. Diethylamine was added for adjusting the pH of the resulting mixture to 11, after which the mixture was aged at a room temperature of 25 °C for 2 weeks to obtain a dimethylpolysiloxane emulsion.
- Then, the dimethylpolysiloxane emulsion was stood under a decompressed pressure of 50 Torr (=̂ 6650 Pa) for 20 minutes for defoaming of the emulsion, after which the emulsion was poured onto a Petri dish having 95 mm diameter and 15 mm depth in order to form a specimen of 2 mm thick. The Petri dish was sealed at its top opening by an aluminum foil to effect preliminarily cooling the specimen at a temperature of -6 °C for 3 hours. Next, the specimen was placed into a freezer maintained at a temperature of - 25 °C and kept for 15 hours to be frozen therein. After removal of the freezer, the specimen was placed in a vacuum chamber of a freeze-dryer available as "VD-80" from "Taitech Corp." to be dried without being defrosted under a vacuum pressure of 0.05 Torr at a cold trap temperature of -80 °C for 6 hours, thereby obtaining a porous silicone membrane of 2 mm thick. The resulting silicone membrane was found to have a number of open cells which have an average diameter of 70 µm and intercommunicated through voids of 3 µm in average diameter. FIGS. 1 and 2 show cross-sections of thus obtained silicone membrane in photomicrographs.
- 100 parts of emulsion A prepared in Example 1 were mixed with 1.5 parts of emulsion B prepared in Example 1, and 25 parts of aqueous dissipation solution of colloidal silica (having a solid content of 30 wt%) as the cross-linking agent to provide a dimethylpolysiloxane emulsion having the pH of 5.5. Thereafter, dimethylpolysiloxane emulsion was frozen and dried in the same manner as in Example 1 to provide a 2 mm thick porous silicone membrane except for that the emulsion has not been aged prior to the freeze-drying. The resulting silicone membrane was found to have a number of open cells having an average diameter of 30 µm and intercommunicated through voids of 1.5 µm in average diameter.
- 100 parts of emulsion A prepared in Example 1 were mixed with 1.5 parts of emulsion B prepared in Example 1, and 3 parts of sodium silicate as a curing catalyst. After being added with diethylamine for pH adjustment to 10, the mixture was aged at a room temperature of 25 °C for 4 weeks to prepare a dimethylpolysiloxane emulsion. Thus obtained emulsion was then frozen and dried in the same manner as in Example 1 to provide a 2 mm thick porous silicone membrane except for that the emulsion has not been aged prior to the freeze-drying. The resulting silicone membrane was found to have a number of open cells having an average diameter of 40 µm and intercommunicated through voids of 1.5 µm in average diameter.
- 100 parts of emulsion A prepared in Example 1 were mixed with 1 part of vinyltrimethoxysilane as a cross-linking agent and 0.1 part of dioctyl-tin-dilaurate as a curing catalyst followed by being stirred into a homogeneous emulsion of dimethylpolysiloxane. Thus obtained emulsion was then frozen and dried in the same manner as in Example 1 to provide a 2 mm thick porous silicone membrane except for that the emulsion has not been aged prior to the freezedrying. The resulting silicone membrane was found to have a number of open cells having an average diameter of 20 µm and intercommunicated through voids of 1 µm in average diameter.
- The dimethylpolysiloxane emulsion prepared in Example 1 was defoamed and poured onto the Petri dish to form a specimen of 2 mm thickness. The specimen was placed in the freezer maintained at a temperature of - 20 °C and kept for 16 hours to be frozen therein. After removing out of the freezer, the specimen was left standing at a room temperature of 25 °C for 6 hours so as to be defrosted into a 2 mm thick silicone membrane saturated with water. Next, thus defrosted silicone membrane was dried within an oven of 70 °C for 20 hours to obtain a 1.1 mm thick porous silicone membrane. The resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 70 µm and also found to have a skin layer on its surface.
- The dimethylpolysiloxane emulsion prepared in Example 2 was treated in the identical manner as in Comparative Example 1 to provide a 1 mm thick porous silicone membrane. The resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 30 µm and also found to have a skin layer on its surface.
- The dimethylpolysiloxane emulsion prepared in Example 3 was treated in the identical manner as in Comparative Example 1 to provide a 1 mm thick porous silicone membrane. The resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 40 µm and also found to have a skin layer on its surface.
- The dimethylpolysiloxane emulsion prepared in Example 4 was treated in the identical manner as in comparative Example 1 to provide a 1.1 mm thick porous silicone membrane. The resulting silicone membrane was found to have a number of minute closed cells having an average diameter of 20 µm and also found to have a skin layer on its surface.
freeze drying said emulsion to obtain said porous silicone product with water being sublimed therefrom, wherein any heating should be avoided at the initial stage of the drying.
Claims (2)
- A process of fabricating a porous silicone product utilizing a water emulsion of an organopolysiloxane, said process comprising the steps of:
preparing an emulsion including:a) a substantially straight chain organopolysiloxane having at least two silanol groups per one molecule;b) a cross-linking agent selected from colloidal silica, alkali metal silicate and hydrolyzable silane and partially hydrolyzed condensate of hydrolyzable silane, having at least three hydrolyzable groups attached to silicon atoms;c) a curing catalyst;d) an emulsifier; ande) water,said emulsion being capable of forming an elastomer by removal of water therefrom; and
freeze drying said emulsion to obtain said porous silicone product with water being sublimed therefrom, wherein any heating should be avoided at the initial stage of the drying. - A process as set forth in claim 1, wherein said freeze drying is carried out after cooling said emulsion to such a temperature as not to freeze said emulsion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP3171190A JP2571881B2 (en) | 1991-07-11 | 1991-07-11 | Method for producing silicone porous body |
JP171190/91 | 1991-07-11 |
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Publication Number | Publication Date |
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EP0522585A1 EP0522585A1 (en) | 1993-01-13 |
EP0522585B1 true EP0522585B1 (en) | 1996-10-02 |
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ID=15918682
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EP92111794A Expired - Lifetime EP0522585B1 (en) | 1991-07-11 | 1992-07-10 | Process of fabricating porous silicone product |
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EP (1) | EP0522585B1 (en) |
JP (1) | JP2571881B2 (en) |
BR (1) | BR9202563A (en) |
DE (1) | DE69214213T2 (en) |
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Also Published As
Publication number | Publication date |
---|---|
JPH06287348A (en) | 1994-10-11 |
DE69214213D1 (en) | 1996-11-07 |
EP0522585A1 (en) | 1993-01-13 |
DE69214213T2 (en) | 1997-02-06 |
BR9202563A (en) | 1993-03-16 |
JP2571881B2 (en) | 1997-01-16 |
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